CN112724322B - Suspension swelling grafting modification method of PVC resin - Google Patents
Suspension swelling grafting modification method of PVC resin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
Abstract
The invention discloses a suspension swelling grafting modification method of PVC resin, which comprises the following steps: (1) adding PVC resin, acrylate, deionized water and a dispersing agent into a reactor, and stirring and reacting at the temperature of 40-70 ℃ for 1-2 hours to obtain a swollen reactant; (2) adding an initiator I into the reactant obtained in the step (1), and continuously dropwise adding an activating agent I into the reactor to obtain a main polymerization reaction product; (3) adding an initiator II into the main polymerization reaction product, continuously dropwise adding an activating agent II into the reactor for 1-1.5 h, and preserving heat for 1-2 h after dropwise adding to obtain a post-polymerization reaction product; (4) and cooling, washing, filtering, drying and sealing the post-polymerization reaction product for storage to obtain the modified PVC resin. The modified PVC resin prepared by the invention greatly reduces the content of residual monomers in the modified PVC resin on the basis of ensuring the processing performance and the mechanical property of the modified PVC resin, the content of the residual monomers is less than 0.19 percent, the odor grade is less than or equal to 1 grade, and the modified PVC resin has wide application prospect.
Description
Technical Field
The invention relates to the technical field of PVC resin modification, in particular to a suspension swelling grafting modification method of PVC resin.
Background
PVC resins are one of the most widely used thermoplastic plastics in the world today, and have been widely used in many fields such as building materials, vehicles, machines, electronics, and electric appliances because of their excellent mechanical and electrical properties and their excellent flame retardancy, transparency, chemical resistance, etc., and particularly, they have been rapidly used in recent years as new chemical building materials. However, since the PVC resin has the problems of poor toughness, poor thermal stability, easy aging and the like, in order to widen the application field of PVC, PVC must be modified to endow PVC with new performance and new application direction. The traditional toughening modification method is to use elastomers such as rubber and the like as modifiers to improve the toughness of the PVC resin, but the traditional toughening modification method usually sacrifices the strength, rigidity, dimensional stability, heat resistance and processability of the PVC resin. In recent years, the PVC molecular structure is changed by chemical modes such as copolymerization, grafting, chlorination, crosslinking and the like, and a flexible molecular chain segment is introduced on a PVC molecular chain, so that the toughness and other properties of PVC are effectively improved, a remarkable effect is obtained, and a wide market prospect is shown.
Wherein the graft modification means a reaction of polymerizing a certain monomer in the presence of a polymer component and grafting a branch polymer component to a main polymer through a chemical bond. PVC graft copolymerization modification is to introduce another monomer group on the side chain of polyvinyl chloride resin, or to carry out copolymerization grafting reaction with another polymer, and graft the monomer onto the polymer with good flexibility, so as to improve the impact resistance of hard products, or improve the plasticization stability of soft products. After graft modification, PVC can be improved in many aspects of properties, such as: mechanical properties, processability, thermal stability, and the like; in addition, special functional groups can be connected to polymer molecules through graft modification to form a functional material with special performance; or the polymer has crosslinking property and reactivity and continuously reacts with other substances to generate new macromolecules.
The general methods for preparing graft copolymers with PVC as the backbone include solution, suspension swelling, melt grafting, solid phase grafting, and mechanochemical grafting. At present, suspension swelling PVC and acrylate graft copolymerization are researched more in a polymerization method, and the graft copolymer of PVC prepared by the grafting method is a graft copolymerization reaction after a framework polymer PVC is fully swelled by using a grafting monomer, and is generally initiated by adopting an initiator, and the reaction is carried out according to a free radical chain transfer mechanism, so that the aim of modification or functionalization is fulfilled. For example, chinese patent publication No. CN105754040A discloses a high-fluidity heat-resistant PVC resin and a preparation method thereof, the high-fluidity heat-resistant PVC resin mainly comprises the following components: the preparation method of the high-fluidity heat-resistant PVC resin comprises the steps of preparing the PVC resin, the bridge compound, the functional monomer and the initiator by adopting a solid-phase chemical reaction method such as microwave irradiation or mechanochemical reaction. However, in the method, in order to improve the conversion rate of the monomer, the swelling adsorption time is not less than 20 hours, when the grafting rate of the PVC resin is not high and the monomer conversion is incomplete, the unreacted modified monomer remains in the resin to cause the resin to have pungent odor, and the residual monomer is further volatilized due to the operation of temperature rise and the like during processing, so that the pungent odor is more obvious.
Disclosure of Invention
The invention aims to solve the technical problem of providing a suspension swelling grafting modification method of PVC resin, which can effectively remove residual monomers after PVC resin grafting modification.
The technical scheme adopted by the invention for solving the technical problems is as follows: a suspension swelling grafting modification method of PVC resin comprises the following steps:
(1) adding PVC resin, acrylate, deionized water and a dispersing agent into a reactor, and stirring and reacting at the temperature of 40-70 ℃ for 1-2 hours to obtain a swollen reactant; the mass of the acrylic ester is 2-10% of that of the PVC resin, the mass of the deionized water is 1-2 times of that of the PVC resin, and the mass of the dispersing agent is 0.05-0.1% of that of the PVC resin;
(2) adding an initiator I into the reactant obtained in the step (1), continuously dropwise adding an activating agent I into the reactor for 2-3 h, and preserving heat for 1-2 h after dropwise adding to obtain a main polymerization reaction product; the adding amount of the initiator I is 5-10% of the mass of the acrylate, and the molar ratio of the initiator I to the activator I is 1-2: 1;
(3) adding an initiator II into the main polymerization reaction product obtained in the step (2), continuously dropwise adding an activating agent II into the reactor for 1-1.5 h, and preserving heat for 1-2 h after dropwise adding to obtain a post-polymerization reaction product; the addition amount of the initiator II is 2.5-5% of the mass of the acrylate, and the molar ratio of the initiator II to the activator II is 1-2: 1;
(4) cooling, washing, filtering, drying and sealing the post-polymerization reaction product obtained in the step (3) for storage to obtain modified PVC resin;
the initiator I and the initiator II are oil-soluble initiators, the activator I is sodium bisulfite or sodium metabisulfite, and the activator II is sodium hydrosulfite or ascorbic acid.
Further, the initiator I and the initiator II are selected from tert-butyl hydroperoxide, dicumyl peroxide or benzoyl peroxide.
Further, the initiator I is benzoyl peroxide, and the initiator II is tert-butyl hydroperoxide.
Further, the mass of the acrylic ester is 5% of that of the PVC resin.
Furthermore, the acrylate is selected from one or more of ethyl acrylate, butyl acrylate and isooctyl acrylate.
Further, the dispersing agent is alkylphenol polyoxyethylene or polyvinyl alcohol.
Further, the molar ratio of the initiator I to the activator I is 1:1, and the molar ratio of the initiator II to the activator II is 2: 1.
Further, the total reaction time of the step (2) is 4 h.
Further, the reaction temperature in the steps (1), (2) and (3) is 70 ℃.
Furthermore, the PVC is SG 5-SG 8 type PVC.
The invention has the beneficial effects that: the modified PVC resin prepared by the invention greatly reduces the content of residual monomers in the modified PVC resin on the basis of ensuring the processing performance and the mechanical property of the modified PVC resin, the content of the residual monomers is less than 0.19 percent, the odor grade is less than or equal to 1 grade, and the modified PVC resin has wide application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
adding 1000g of deionized water, 600gSG8 type PVC resin, 30g of isooctyl acrylate and 0.30g of polyvinyl alcohol into a 2L four-neck flask with a condensing device, starting stirring (200r/min), swelling for 1h at a constant temperature of 70 ℃, then adding 1.5g of initiator I (benzoyl peroxide) at one time, slowly dropwise adding 1.18g of prepared activator I (sodium metabisulfite), dropwise adding for 3h, keeping the temperature and reacting for 1h, and controlling the total polymerization time to be 4 h; and after the reaction is finished, 0.75g of initiator II (tert-butyl hydroperoxide) is added in one step, 0.74g of prepared activator II ascorbic acid is continuously dripped, the dripping time is 1h, the reaction is stopped after the heat preservation reaction is carried out for 2h, the reaction system is cooled to the room temperature, all reaction products are transferred to a Buchner funnel, are fully washed by deionized water and are filtered, are placed at 50 ℃ for forced air drying for 48h, and are sealed and stored in a cool and dry environment at the room temperature, so that the modified PVC resin is obtained.
Example 2:
adding 1000g of deionized water, 600gSG8 type PVC resin, 30g of isooctyl acrylate and 0.30g of polyvinyl alcohol into a 2L four-neck flask with a condensing device, starting stirring (200r/min), swelling for 1h at a constant temperature of 50 ℃, then adding 1.5g of initiator I (benzoyl peroxide) at one time, slowly dropwise adding 0.65g of prepared activator I sodium bisulfite, dropwise adding for 3h, keeping the temperature for reaction for 1h, and controlling the total polymerization time to be 4 h; and after the reaction is finished, 0.75g of initiator II (tert-butyl hydroperoxide) is added in one step, 0.73g of prepared activator II sodium dithionite is continuously dripped, the dripping time is 1.5h, the reaction is stopped after the reaction is carried out for 2h under heat preservation, the reaction system is cooled to room temperature, all reaction products are transferred to a Buchner funnel, fully washed by deionized water and filtered, placed at 50 ℃ for forced air drying for 48h, and sealed and stored in a cool and dry environment at room temperature, and the modified PVC resin is obtained.
Example 3:
adding 1000g of deionized water, 600gSG8 type PVC resin, 30g of isooctyl acrylate and 0.30g of polyvinyl alcohol into a 2L four-neck flask with a condensing device, starting stirring (200r/min), swelling for 1h at a constant temperature of 60 ℃, then adding 1.5g of initiator I (benzoyl peroxide) at one time, slowly dropwise adding 1.18g of prepared activator I sodium metabisulfite, dropwise adding for 2.5h, keeping the temperature and reacting for 1.5h, and controlling the total polymerization time to be 4 h; and after the reaction is finished, 0.75g of initiator II (tert-butyl hydroperoxide) is added in one step, 0.74g of prepared activator II ascorbic acid is continuously dripped, the dripping time is 1h, the reaction is stopped after the heat preservation reaction is carried out for 2h, the reaction system is cooled to the room temperature, all reaction products are transferred to a Buchner funnel, are fully washed by deionized water and are filtered, are placed at 50 ℃ for forced air drying for 48h, and are sealed and stored in a cool and dry environment at the room temperature, so that the modified PVC resin is obtained.
Comparative example 1: (same as example 1, no post-polymerization)
Adding 1000g of deionized water, 600gSG8 type PVC resin, 30g of isooctyl acrylate and 0.30g of polyvinyl alcohol into a 2L four-neck flask with a condensing device, starting stirring (200r/min), swelling for 1h at a constant temperature of 70 ℃, then adding 1.5g of initiator I (benzoyl peroxide) at one time, slowly dropwise adding 1.18g of prepared activator I (sodium metabisulfite), dropwise adding for 3h, keeping the temperature for reaction for 1h, stopping the reaction after controlling the total polymerization time to be 4h, cooling the reaction system to room temperature, transferring all reaction products into a Buchner funnel, fully washing and filtering by using deionized water, placing at 50 ℃ for forced air drying for 48h, and sealing and storing in a normal-temperature and cool dry environment to obtain the modified PVC resin.
Comparative example 2: (in the same manner as in example 1, the initiator and the activator were added simultaneously in the same manner and the time for the polymerization was the sum of the time for the preceding and subsequent polymerization reactions)
Adding 1000g of deionized water, 600gSG8 type PVC resin, 30g of isooctyl acrylate and 0.30g of polyvinyl alcohol into a 2L four-neck flask with a condensing device, starting stirring (200r/min), swelling for 1h at a constant temperature of 70 ℃, then adding 1.5g of initiator I (benzoyl peroxide) and 0.75g of initiator II (tert-butyl hydroperoxide) at one time, slowly dropwise adding 1.18g of prepared activator I (sodium metabisulfite) and 0.74g of activator II ascorbic acid, dropwise adding for 4h, stopping the reaction after reacting for 3h under heat preservation, cooling the reaction system to room temperature, transferring all reaction products into a Buchner funnel, fully washing and filtering with deionized water, placing at 50 ℃ for forced air drying for 48h, and sealing and storing under a normal-temperature, shady and dry environment to obtain the modified PVC resin.
Comparative example 3: (same as example 1, the activator added in the postpolymerization was the same as the activator added in the postpolymerization)
Adding 1000g of deionized water, 600gSG8 type PVC resin, 30g of isooctyl acrylate and 0.30g of polyvinyl alcohol into a 2L four-neck flask with a condensing device, starting stirring (200r/min), swelling for 1h at a constant temperature of 70 ℃, then adding 1.5g of initiator I (benzoyl peroxide) at one time, slowly dropwise adding 1.18g of prepared activator I (sodium metabisulfite), dropwise adding for 3h, keeping the temperature and reacting for 1h, and controlling the total polymerization time to be 4 h; and after the reaction is finished, 0.75g of initiator II (tert-butyl hydroperoxide) is added in one step, 0.59g of prepared activator II (sodium metabisulfite) is continuously dripped, the dripping time is 1h, the reaction is stopped after the reaction is carried out for 2h under heat preservation, the reaction system is cooled to the room temperature, all reaction products are transferred to a Buchner funnel, fully washed by deionized water and filtered, the Buchner funnel is placed at 50 ℃ for air blast drying for 48h, and the Buchner funnel is sealed and stored in a normal-temperature cool and dry environment to obtain the modified PVC resin.
Comparative example 4: (same as example 1, the activator added in the postpolymerization was the same as the activator added in the postpolymerization)
Adding 1000g of deionized water, 600gSG8 type PVC resin, 30g of isooctyl acrylate and 0.30g of polyvinyl alcohol into a 2L four-neck flask with a condensing device, starting stirring (200r/min), swelling for 1h at a constant temperature of 70 ℃, then adding 1.5g of initiator I (benzoyl peroxide) at one time, slowly dropwise adding 0.55g of prepared activator I (ascorbic acid), dropwise adding for 2h, keeping the temperature and reacting for 2h, and controlling the total polymerization time to be 4 h; and after the reaction is finished, 0.75g of initiator II (tert-butyl hydroperoxide) is added in one step, 0.74g of prepared activator II ascorbic acid is continuously dripped, the dripping time is 1h, the reaction is stopped after the heat preservation reaction is carried out for 2h, the reaction system is cooled to the room temperature, all reaction products are transferred to a Buchner funnel, are fully washed by deionized water and are filtered, are placed at 50 ℃ for forced air drying for 48h, and are sealed and stored in a cool and dry environment at the room temperature, so that the modified PVC resin is obtained.
First, residual monomer testing method
(1) The modified PVC resins obtained in examples 1 to 3 and comparative examples 1 to 4 were placed in a cartridge of filter paper, and m was accurately weighed1(ii) a Carefully place it in a soxhlet extractor;
(2) cyclohexane is used as an organic solvent for extraction treatment, all parts of an extractor are connected, condensed water is communicated, and extraction treatment is carried out for 24 hours at the constant temperature of 100 ℃; wherein the weight-volume ratio of the PVC resin to the cyclohexane is 1:10 (g/mL);
(3) after the extraction treatment is finished, taking out the filter paper sleeve, then drying until the weight of the filter paper sleeve is unchanged, and accurately weighing m2And recording the mass m of the corresponding extract.
The extraction liquid obtained above is subjected to residual monomer test by an external standard method by adopting an SP3420 gas chromatograph of North Branch Rayleigh, and the test conditions are as follows: the temperature of a column box is 230 ℃, the temperature of a sample inlet is 240 ℃, the temperature of an FID detector is 240 ℃, the split ratio is 30:1, nitrogen is blown into a tail, and the sample injection volume is 1.0 mu L. The residual monomer content detected was recorded and the results are shown in table 1 below.
TABLE 1 test results of examples and comparative examples
Note: the plasticizing time of the original powder SG8PVC resin is 3.38min, the equilibrium torque is 10.24Nm, the tensile strength is 51.79Mpa, the elongation at break is 33.43 percent, and the impact strength is 2.689kJ/m2。
Second, odor intensity testing method
The modified PVC resins obtained in examples 1 to 3 and comparative examples 1 to 4 were subjected to odor grade test according to GB/T28006-2011, wherein the odor intensity is represented by 6-grade intensity representation, and the odor intensity and the intensity of each grade are described in Table 2. The odor level detected was recorded and the results are shown in table 1 below.
TABLE 2 odor rating representation
| Grade level | State description |
| Level 0 | Has no odor |
| Level 1 | Slight smell |
| Stage 2 | Has good taste but no irritation |
| Grade 3 | Has pungent odor |
| 4 stage | Strong pungent smell |
| Grade 5 | Intolerable taste |
Third, processing performance testing method
The modified PVC resins obtained in examples 1-3 and comparative examples 1-4 were respectively tested for processability by HAAKE Torque rheometer, and the resins, stabilizers, lubricants 100:3.5:0.5 (weight fraction) were mixed in a high speed mixer for 1min to prepare a premix, wherein the test was carried out by feeding about 70g, the test temperature was 180 ℃, the rotation speed was 40r/min, and the banburying time was: and (5) recording a torque-time curve of the material for 10min to obtain the balance torque, wherein 2 parallel batches are carried out each time. The adopted stabilizer is a calcium zinc stabilizer, and the lubricant is calcium stearate.
Respectively adding the modified PVC resin premix obtained in the examples 1-3 and the comparative examples 1-4 into an open mill for plasticizing, and controlling the temperature at 175 ℃; and (3) tabletting the plasticized sample by using a vulcanizer, controlling the temperature at 180 ℃, preheating for 10min, pressurizing for 10min under 20MPa, cold-press molding for 3min (pressure of 20MPa), and finally preparing a tensile strength and impact strength test sample strip by using a cutting machine. Tensile Properties determination of tensile Properties according to GB/T1040.2-2006 "tensile Properties of plastics part 2: test conditions for molded and extruded plastics test, type B specimen, tensile plastics 5 mm/min; the impact strength is measured according to GB/T1043.1-2008' impact performance of plastic simply supported beam part 1: the sample size is 80mm multiplied by 10mm multiplied by 4mm, and the testing temperature is 23-25 ℃ when tested by non-instrumented impact test. The results of the tests are shown in table 1.
As can be seen from Table 1, the modified PVC resin obtained in examples 1-3 has a greatly reduced content of residual monomers therein, which is less than 0.19%, while ensuring the processability and mechanical properties thereof.
Claims (10)
1. A suspension swelling graft modification method of PVC resin is characterized by comprising the following steps:
(1) adding PVC resin, acrylate, deionized water and a dispersing agent into a reactor, and stirring and reacting at the temperature of 40-70 ℃ for 1-2 hours to obtain a swollen reactant; the mass of the acrylic ester is 2-10% of that of the PVC resin, the mass of the deionized water is 1-2 times of that of the PVC resin, and the mass of the dispersing agent is 0.05-0.1% of that of the PVC resin;
(2) adding an initiator I into the reactant obtained in the step (1), continuously dropwise adding an activating agent I into the reactor for 2-3 h, and preserving heat for 1-2 h after dropwise adding to obtain a main polymerization reaction product; the adding amount of the initiator I is 5-10% of the mass of the acrylate, and the molar ratio of the initiator I to the activator I is 1-2: 1;
(3) adding an initiator II into the main polymerization reaction product obtained in the step (2), continuously dropwise adding an activating agent II into the reactor for 1-1.5 h, and preserving heat for 1-2 h after dropwise adding to obtain a post-polymerization reaction product; the addition amount of the initiator II is 2.5-5% of the mass of the acrylate, and the molar ratio of the initiator II to the activator II is 1-2: 1;
(4) cooling, washing, filtering, drying and sealing the post-polymerization reaction product obtained in the step (3) for storage to obtain modified PVC resin;
the initiator I and the initiator II are oil-soluble initiators, the activator I is sodium bisulfite or sodium metabisulfite, and the activator II is sodium hydrosulfite or ascorbic acid.
2. The method for the suspension swelling graft modification of PVC resin according to claim 1, wherein: the initiator I and the initiator II are selected from tert-butyl hydroperoxide, dicumyl peroxide or benzoyl peroxide.
3. The method for the suspension swelling graft modification of PVC resin according to claim 2, wherein: the initiator I is benzoyl peroxide, and the initiator II is tert-butyl hydroperoxide.
4. The method for the suspension swelling graft modification of PVC resin according to claim 1, wherein: the mass of the acrylic ester is 5% of that of the PVC resin.
5. The method for the suspension swelling graft modification of PVC resin according to claim 1 or 4, wherein: the acrylate is selected from one or more of ethyl acrylate, butyl acrylate and isooctyl acrylate.
6. The method for the suspension swelling graft modification of PVC resin according to claim 1, wherein: the dispersant is alkylphenol polyoxyethylene or polyvinyl alcohol.
7. The method for the suspension swelling graft modification of PVC resin according to claim 1, wherein: the molar ratio of the initiator I to the activator I is 1:1, and the molar ratio of the initiator II to the activator II is 2: 1.
8. The method for the suspension swelling graft modification of PVC resin according to claim 1, wherein: the total reaction time of the step (2) is 4 h.
9. The method for the suspension swelling graft modification of PVC resin according to claim 1, wherein: the reaction temperature of the steps (1), (2) and (3) is 70 ℃.
10. The method for the suspension swelling graft modification of PVC resin according to claim 1, wherein: the PVC is SG 5-SG 8 type PVC.
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